Paper Release Compositions Having Improved Adhesion to Paper and Polymeric Films

ABSTRACT

The present invention relates to curable alkenyl based silicone release coating compositions having improved adhesion to paper and polymeric substrates. Furthermore the present invention relates to the process for making a silicone release coating with improved adhesion to paper and polymeric substrates.

FIELD OF THE INVENTION

The present invention relates to curable alkenyl based silicone releasecoating compositions having improved adhesion to paper and polymericsubstrates. The present invention also relates to additives that improveadhesion of silicone release coating compositions to paper and polymericsubstrates. Furthermore the present invention relates to the process formaking a silicone release coating with improved adhesion to paper andpolymeric substrates.

BACKGROUND OF THE INVENTION

Curable silicone compositions are applied to substrates to aid in therelease of adhesive materials thereon. Laminates comprising a releasecoated paper or polymeric film with a pressure sensitive adhesive and asheet material that can be a decorative lamina or label are used bystripping off the release liner, which is discarded, and affixing thelamina or label onto a surface.

Typically these release compositions cure by one of two mechanisms,thermal curing or photo-catalytic curing. Thermally curing releasesystems generally are comprised of the following compositions:

-   -   (A) a linear alkenyl substituted polysiloxane polymer that is        the primary component or base polymer of the curable        composition;    -   (B) a hydride functional cross-linking silicone, typically a        methyl hydrogen siloxane polymer, copolymer or oligomer;    -   (C) an addition cure hydrosilylation catalysts, typically either        a platinum or rhodium based catalyst;    -   (D) a cure inhibiting compound or mixtures thereof to increase        the useful life of the coating bath.

The alkenyl functional silicone polymer release compositions typicallyused fall into one of two categories:

-   -   1) a linear alkenyl chain-stopped polymer:

M^(vi)D_(x)M^(vi)   4)

where M^(vi) indicates an alkenyl chain-stopping M group or

-   -   2) multi-functional alkenyl copolymers:

M^(vi)D_(x)D^(vi) _(y)M^(vi)   5)

where D^(vi) indicates an alkenyl substituted D group. The alkenyl chainstopped polymers, M^(vi)D_(x)M^(v), generally cure faster than themulti-functional copolymers, M^(vi)D_(x)D^(vi) _(y)M^(vi). As releasecomposites are delaminated, the formulations based on the linear alkenylchain-stopped polymers show significant increases in the delaminatingforce necessary as delaminating speed increases. In contrast, while themulti-functional alkenyl polymers tend to have a slower curing speed theincrease in delaminating force with increasing delaminating speed is notnearly as great proportionately.

While the general practice usually employs linear base polymers, (A),solventless, high solids content formulations have been described. Asdescribed in U.S. Pat. No. 4,448,815 ('815) a linear alkenyl siloxanebase copolymer is a copolymer of:

(1) R_(c)R_(d) ¹Si_((4−c−d)/2)   1)

where R is generally an alkyl radical, R¹ is a low molecular weightolefinic substituent such as vinyl or allyl, c has value from 0 to 2 andthe average of value of the sum c+d is 0.8 to 3; and

(2) R_(n)SiO_((4−n)/2)   2)

where R is generally an alkyl radical and n has a value of 0.8 to 2.5.The preferred base copolymer of the '815 patent has the following linearstructure:

(H₂C═CH)R₂Si—O—(R₂Si—O—)_(i)—(RR¹Si—O—)_(j)—SiR₂(H₂C═CH)

where the subscripts i and j are integers.

U.S. Pat. No. 4,774,111 ('111) describes a variation of the above linearcopolymer where the R group in formula 2 is selected from alkyl andalkenyl radicals. The polymer of the '111 patent is defined as beingsubstantially linear, i.e. having no more than a trace amount of T or Qgroups. This substantially linear requirement for alkenyl functionalheat curing silicone release compositions is repeated in U.S. Pat. Nos.4,772,515; 4,783,552 and 5,036,117.

In contrast, the possibility of branched alkenyl polymers is admitted bythe structural formulas recited in U.S. Pat. No. 4,057,596 ('596). Inthe '596 patent the composition comprises:

-   -   (A′) a substantially linear vinyl chain stopped polymer;    -   (B′) a linear methyl hydrogen polymer;    -   (C′) a methyl vinyl polysiloxane having at least three vinyl        groups per molecule;    -   (D′) a methyl hydrogen polysiloxane having at least three        hydride hydrogen atoms per molecule; and    -   (E′) a platinum hydrosilylation catalyst.

Component (C′) is described in the '596 patent as containing(H₂C═CH)(CH₃)SiO_(2/2) (D^(vi)), (H₂C═CH)(CH₃)₂SiO_(1/2) (M^(vi)), and(H₂C═CH)SiO_(3/2) (T^(vi)), units either singly or in combination with(CH₃)₂SiO_(2/2) (D), (CH₃)₃SiO_(1/2) (M), and (CH₃)SiO_(3/2) (T). Theoptional inclusion of vinyl substituted T units and methyl T unitspermits the composition of the '596 patent to possess branchedstructures.

U.S. Pat. No. 4,386,135 describes a terminally unsaturated siliconepolymer having the formula

R_(4−a)Si((R₂SiO—)_(b)OSiR₂R²)_(a)   3)

where a may be 2, 3, or 4. When a=4 the formula produces a Q resin. Whena=3, a T structure results and the structure possesses only a singlebranch point. When a=2, the formula devolves to an alkenyl chain stoppedlinear polymer.

U.S. Pat. No. 5,468,826 teaches adhesion promoting additives comprisedof organosiloxane copolymers having SiO_(4/2) units, alkoxy functionalgroups, epoxy or acryloxyalky groups and silicon hydride functionality.To those skilled in the art, it can be readily recognized that thesehave the disadvantage of increasing the release force during thedelaminating process due to the resinous nature of the additivepreventing low release force coatings from being available.

U.S. Pat. No. 3,873,334 teaches adhesion promoting additives comprisedof acyloxy functional silanes, which additionally have silicon hydrideor alkenyl functionality respectively. However, the acyloxy groupliberated has the disadvantages of inhibiting addition cure, thereforeslowing the addition curing process; liberating corrosive andobjectionable odor hydrolysis products during the coating process.Furthermore, the acyloxy groups remaining in the release coatinghydrolyzed over resulting in an undesirable interaction with theadhesive thus leading to undesirable delaminating release properties.

U.S. Pat. No. 5,567,764 teaches alkoxy containing alkenyl functionalorganopolysiloxanes as adhesion promoters for release coating ontopolymeric films.

European patent 057984A2 teaches meth(acryl)oxy functional alkoxysilanesas adhesion promoters for release coatings on polymeric films.

Despite the above cited patents there still remains a need in theindustry for release coating compositions, adhesion promoting additiveswhich address the disadvantages of either stable adhesion to both paperand polymeric films, exhibit non-inhibiting effect on the curing, notliberate corrosive hydrolysis products, not exhibit objectionable odorduring manufacturing of the laminate construction, not have hydrolysisproducts that would adversely interact with the adhesive used in thelaminating construction, and a cost effective reproducible method ofmanufacture.

SUMMARY OF THE INVENTION

The present invention provides for a release coating additive for arelease coating that provides adhesion to paper and polymeric films thatdoes not inhibit the addition cure process, that does not liberatecorrosive hydrolysis products, that does not exhibit an objectionableOdor during the manufacturing of the laminate construction and that doesnot liberate hydrolysis products which adversely interact with theadhesive used in the laminating construction. Furthermore, the presentinvention also provides for a process of making an additive exhibitingstable adhesion on paper and polymeric films when added to a releasecoating.

The release compositions of the present invention comprise additives forimproved anchorage of release coatings comprising:

(R_(a)SiO_((4−a)/2))_(n)

where n is an integer greater than 3, a is from 1 to 3, R is an oxiraneor epoxide, or carboxylic add anhydride containing radical having fromone to forty carbon atoms, monovalent hydrocarbon or hydrocarbonoxyradicals, hydride atoms, and with at least one oxirane or epoxide, orcarboxylic add anhydride and hydride being present on the molecule.

The compositions of the present invention further comprise a curablealkenyl silicone having the formula:

M^(vi) _(a)T_(b)D_(c)M_(d)

where

M^(vi)=R¹ _(3−p)R² _(p)SiO_(1/2), where R¹ is selected from the groupconsisting of one to forty carbon monovalent hydrocarbon radicals and R²is selected from the group consisting of two to forty carbon atomterminal olefinic monovalent hydrocarbon radicals, where p varies from 1to 3;

T=R³SiO_(3/2) where R³ is selected from the group consisting of R¹ andR²;

D=R⁴R⁵SiO_(2/2) where R⁴ and R⁵ are each independently selected from thegroup consisting of R¹ and R²; and

M=R¹ ₃SiO_(1/2) where each R¹ is as previously defined and isindependently selected; wherein a and b have values ranging from about 2to about 5, c is an integer ranging from about 50 to about 1,000 and dhas a value ranging from 0 to 0.5, preferably from 0.25 to about 0.5,more preferably from about 0.35 to about 0.5 and most preferably fromabout 0.4 to about 0.5; which composition is preferably crosslinked by asubstantially linear hydrogen siloxane selected from the group ofcompounds:

MD_(e)D′_(f)M,

MD′_(f)M,

MD_(e)D′_(f)M′,

M′D_(e)D′_(f)M′, and

M′D_(e)M′

where

M=R′₃SiO_(1/2),

M′=H_(g)R′_(3−g)SiO_(1/2), and

D=R′R′SiO_(2/2), and

D′=R′HSiO_(2/2) wherein each R′ in M, M′, D, and D′ is independentlyselected from the group consisting of one to forty carbon monovalenthydrocarbon radicals wherein the subscripts e and f may be zero orpositive whereby the sum of e and f ranges from about 10 to about 100subject to the limitation that the sum of f and g is two or greater. Thesubstantially linear hydrogen siloxane is preferably selected from thegroup consisting of

MD_(e)D′_(f)M,

MD′_(f)M,

and mixtures thereof.

Preferably the substituents, R¹, of the curable alkenyl silicone aremethyl, trifluoropropyl or phenyl and R² is preferably selected from thegroup consisting of two to ten carbon atom alkenyl groups.

Further, in the substantially linear hydrogen siloxane R′ is preferablymethyl, trifluoropropyl or phenyl.

The compositions of the present invention may be utilized as asolventless composition, a composition diluted by a suitable solvent, oras an aqueous emulsion and find particular use in release compositionsfor paper and polymeric films.

DETAILED DESCRIPTION OF THE INTENTION

Release coatings are part of a laminate wherein a release coating iscoated upon a substrate. Generally substrates suitable for releasecoatings are selected from the group consisting of paper, polymericfilms such as those consisting of polyethylene, polypropylene, andpolyester.

The release compositions of the present invention comprise additives forimproved anchorage of release coatings comprising additives for improvedanchorage of release coatings comprising:

(R_(a)SiO_((4−a)/2))_(n)

where n is an integer greater than 3, a is from 1 to 3, R is an oxiraneor epoxide, or carboxylic acid anhydride containing radical having fromone to forty carbon atoms, monovalent hydrocarbon or hydrocarbonoxyradicals, hydride atoms, and with at least one oxirane or epoxide, orcarboxylic acid anhydride and hydride being _(p)resent on the molecule.

The present invention further provides for an alkenyl curable siliconecomposition of the formula

M^(vi) _(a)T_(b)D_(c)M_(d)

where

M^(vi)=R¹ _(3−p)R² _(p)SiO_(1/2), where R¹ is selected from the groupconsisting of one to forty carbon monovalent hydrocarbon radicals and R²is selected from the group consisting of two to forty carbon atomolefinic monovalent hydrocarbon radicals, where p ranges from 1 to 3;T=R³SiO_(3/2) where R³ is selected from the group consisting of R¹ andR², D=R⁴R⁵SiO_(2/2) where R⁴ and R⁵ are each independently selected fromthe group consisting of R¹ and R², and M=R¹ ₃SiO_(1/2) where each R¹ isindependently selected and the subscripts a and b have values rangingfrom about 2 to about 5 and c is an integer ranging from about 50 toabout 1,000 and d has a value ranging from 0 to 0.5, preferably from0.25 to about 0.5, more preferably from about 0.35 to about 0.5 and mostpreferably from about 0.4 to about 0.5. Applicants define the termsubstantially branched to mean that the average number of T branchingsites per alkenyl silicone molecule of (A) is at least two andpreferably three.

The release compositions of the present invention comprise:

(A) additives for improved anchorage of release coatings comprising:

(R_(a)SiO_((4−a)/2))_(n)

where n is an integer greater than 3, a is from 1 to 3, R is an oxiraneor epoxide, or carboxylic acid anhydride containing radical having fromone to forty carbon atoms, monovalent hydrocarbon or hydrocarbonoxyradicals, hydride atoms, and with at least one oxirane or epoxide; orcarboxylic acid anhydride and hydride being present on the molecule and

(B) an alkenyl silicone having the formula:

M^(vi) _(a)T_(b)D_(c)M_(d)

where the subscripts a, b, c, and d are as previously defined;

(C) a hydrogen siloxane selected from the group of compounds:

MD_(e)D′_(f)M

MD′_(f)M,

MD_(e)D′_(f)M′

M′D_(e)D′_(f)M′,

and

M′D_(e)M′

where M is as previously defined and

M′=H_(g)R′_(3−g)SiO_(1/2)

D=R′R′SiO_(2/2) where each R′ is independently selected and

D′=R′HSiO_(2/2)

where R′ is as previously defined, the subscripts e and f may be zero orpositive wherein the sum of e and f ranges from about 10 to about 100subject to the limitation that the sum of f and g is two or greater and

(D) a hydrosilylation catalyst comprising a metal selected from thegroup consisting of nickel, palladium, platinum, rhodium, iridium,ruthenium and osmium; and

(E) a cure inhibitor.

The amount of component (A) that is used in this invention range fromabout 0.1 to 5.0 parts, preferably from 0.5 to 4.0, and more preferablyfrom about 0.5 to 3.0 parts.

The amounts of Components (B) and (C) that are used in the compositionsof this invention are not narrowly limited. Said amounts, expressed interms of the ratio of the number of silicon-bonded hydrogen atoms ofComponent (B) to the number of silicon-bonded olefinic hydrocarbonradicals of Component (A), as is typically done, are sufficient toprovide a value for said ratio of from 1/100 to 100/1, usually from 1/20to 20/1, and preferably from 1/2 to 20/1.

Broadly stated, Component (D) of the composition of this invention is acatalyst component which facilitates the reaction of the silicon-bondedhydrogen atoms of Component (C) with the silicon-bonded olefinichydrocarbon radicals of Component (B) and can be any platinum-containingcatalyst component. For example, Component (D) can be platinum metal; acarrier such as silica gel or powdered charcoal, bearing platinum metal;or a compound or complex of a platinum metal.

A typical platinum-containing catalyst component in theorganopolysiloxane compositions of this invention is any form ofchloroplatinic acid, such as, for example, the readily availablehexahydrate form or the anhydrous form, because of its easydispensability in organosiloxane systems. A particularly useful form ofchloroplatinic acid is that composition obtained when it is reacted withan aliphatically unsaturated organosilicon compound such asdivinyltetramethyldisiloxane, as disclosed by U.S. Pat. No. 3,419,593incorporated herein by reference.

The amount of platinum-containing catalyst component that is used in thecompositions of this invention is not narrowly limited as long as thereis a sufficient amount to accelerate a room temperature reaction betweenthe silicon-bonded hydrogen atoms of Component (C) with thesilicon-bonded olefinic hydrocarbon radicals of Component (B). The exactnecessary amount of said catalyst component will depend upon theparticular catalyst and is not easily predictable. However, forchloroplatinic acid said amount can be as low as one part by weight ofplatinum for every one million parts by weight of organosiliconComponents (B) plus (C). Preferably said amount is at least 10 parts byweight, on the same basis.

For compositions of this invention which are to be used in the coatingmethod of this invention, the amount of platinum-containing catalystcomponent to be used is preferably sufficient to provide from 10 to 500parts by weight platinum per one million parts by weight oforganopolysiloxane components (B) plus (C).

The hydrosilylation catalyst is selected from the group consisting ofcatalysts comprising a metal selected from the group consisting ofnickel, palladium, platinum, rhodium, iridium, ruthenium and osmium oras taught in U.S. Pat. Nos. 3,159,601; 3,159,662; 3,419,593; 3,715,334;3,775,452 and 3,814,730.

Inhibitors, component (E), for the platinum group metal catalysts arewell known in the organosilicon art. Examples of various classes of suchmetal catalyst inhibitors include unsaturated organic compounds such asethylenically or aromatically unsaturated amides, U.S. Pat. No.4,337,332; acetylenic compounds, U.S. Pat. Nos. 3,445,420; 4,347,346 and5,506,289; ethylenically unsaturated isocyanates, U.S. Pat. No.3,882,083; olefinic siloxanes, U.S. Pat. No. 3,989,667; unsaturatedhydrocarbon diesters, U.S. Pat. Nos. 4,256,870; 4,476,166 and 4,562,096,and conjugated ene-ynes. U.S. Pat. Nos. 4,465,818 and 4,472,563; otherorganic compounds such as hydroperoxides, U.S. Pat. No. 4,061,609;ketones, U.S. Pat. No. 3,418,731; sulfoxides, amines, phosphines,phosphites, nitriles, U.S. Pat. No. 3,344,111; diaziridines, U.S. Pat.No. 4,043,977; half esters and half amides, U.S. Pat. No. 4,533,575; andvarious salts, such as U.S. Pat. No. 3,461,185. It is believed that thecompositions of this invention can comprise an inhibitor from any ofthese classes of inhibitors.

The inhibitors may be selected from the group consisting ofethylenically unsaturated amides, aromatically unsaturated amides,acetylenic compounds, ethylenically unsaturated isocyanates, olefinicsiloxanes, unsaturated hydrocarbon diesters, unsaturated hydrocarbonmono-esters of unsaturated acids, conjugated ene-ynes, hydroperoxides,ketones, sulfoxides, amines, phosphines, phosphites, nitriles, anddiaziridines.

Preferred inhibitors for the compositions of this invention are themaleates and alkynyl alcohols.

The amount of Component (E) to be used in the compositions of thisinvention is not critical and can be any amount that will retard theabove-described platinum-catalyzed hydrosilylation reaction at roomtemperature while not preventing said reaction at moderately elevatedtemperature, i.e. a temperature that is 25 to 50° C. above roomtemperature. No specific amount of inhibitor can be suggested to obtaina specified bath life at room temperature since the desired amount ofany particular inhibitor to be used will depend upon the concentrationand type of the platinum group metal-containing catalyst, the nature andamounts of Components (A) and (B). The range of Component (E) can be0.1-10% by weight, preferably 0.15-2% by weight, and most preferably0.2-1% by weight.

The compositions of the present invention may be used as formulationsthat are free of solvent, i.e. 100% solids, diluted with an organicsolvent that is miscible, or as an aqueous emulsion. When theformulation of the present invention is used as a solventless coating,it is preferred that the viscosity of the alkenyl silicone be in a rangevarying from about 100 to about 10,000 centipoise, preferably from about125 to about 1,000, more preferably from about 150 to about 500, andmost preferably from about 200 to about 300 centipoise. This is mosteasily accomplished by manipulation of the ratios of the stoichiometricsubscripts between the terminal M and M^(vi) groups and the T groups inthe formula:

M^(vi) _(a)T_(b)D_(c)M_(d)

with one general consideration being that a+d>b. If this condition isnot met, the alkenyl silicone can become much more viscous. This doesnot preclude use of the silicone as a release coating material becausethe silicone may be dispersed or dissolved in a suitable solvent andcoated thereby.

It is generally appreciated that other components may be added to thecompositions of the present invention such as bath life extenders astaught in U.S. Pat. Nos. 5,036,117 and 5,516,558; release additives forincreasing the release force; fillers, extenders, reactive diluents,anchorage additives that improve adhesion to specific substrates, andthe like.

When used as emulsions, the silicones of the present invention aregenerally emulsified by the addition of non-ionic surfactants, additionof water followed by processing in a colloid mill.

All United States patents referenced herein are herewith and herebyspecifically incorporated by reference.

EXPERIMENTAL

The following examples are designed to illustrate the present inventionand are not to be construed as limiting the invention as embodied inthese specific examples.

Example 1 Preparation of Anchorage Additive:

A mixture of allyl glycidyl ether (AGE) (Aldrich, 2.886 g, 25.3 mmol)and polymethylhydrosiloxane (2.97 g, SiH=47.5 mmol) was diluted withtoluene (50 mL) and stirred with 0.61×10⁻⁴ ppm platinum at roomtemperature. A small exothermic effect was observed after about 10 min.Progress of the reaction was followed by ¹H NMR—after 1 hr 25% of Si—Hgroups were converted to Si—C bonds. In order to increase conversion ofSi—H bonds, the mixture was stirred further for additional 24 hrs.Toluene was evaporated and the residue was characterized by NMR and GPCusing CH₂Cl₂ as an eluent ( M _(n)=11100, M _(w)=39100, M _(w)/ M_(n)=3.52). Purified product (5.4 g) was obtained with 95% yield. ¹H NMR(CDCl₃): δ/ppm=0.1 (s, OSi(CH₃)₃, terminal), 0.2 (s, —OSi(CH₃)O—), 0.5(m, CH₂,), 1.65 (m, CH₂,), 2.6 and 2.8 (m, CH₂,) 3.1 (m, CH), 3.45 (m,CH₂,), 3.4 and 3.7 (m, CH₂,), 4.7 (m, SiH). ²⁹Si NMR (CDCl₃): δ/ppm=from−34 to −38 (—OSiMeHO—), −19 to −23 (—SiMe(CH₂)O—), 10 (—OSiMe₃).

Release Coating with Anchorage Additive:

A release coating formulation prepared by mixing:

¹SL6626 5.0 g ¹SS4300c 0.16 g  Example 1 0.1 g ¹GE Silicones solventlesspaper release product

This coating formulation above was coated² onto 142 gauge polyester film(PET) corona treated to 54 dyne cm. Samples were cured for the times andthe temperatures shown in Table 1 below. These were evaluated after 1hour and 3 days room temperature aging for anchorage by a finger rub-offmethod. ² Black Clawson Converting Machinery LLC, Fulton, N.Y.

TABLE 1 Abrasive test of PET films 100° C. 120° C. Cure Time, Rub-offtest Rub-off test seconds 1 hr 3 days 1 hr 3 days 10 −− − +/− +++ 20 +/−+/− +/− +++ 30 +/− ++ +/− +++ 40 −− +/− +/− +++ 60 −− +/− +/− +++

Efficiency of attachment by “Rub-off” was rated as follows:

very weakly attached −−− weakly attached −− could be removed but notvery easily +/− strongly attached ++ very strongly attached +++

Example 2 Preparation of Anchorage Additive:

A mixture of allyl glycidyl ether (AGE) (Aldrich, 142.7 g, 1.25 mol) andpolymethylhydrosiloxane (150.0 g, SiH=1.6 wt %) and 20 ppm rhodium usingan ethanol solution of tris(dibutylsulfide)rhodium(III)trichloridecontaining 1.2 wt % rhodium at 120-130° C. after an exotherm to 170° C.for 4 hours. The reaction mixture was filtered then vacuum stripped at120° C. to yield a 450 cstks reaction product having 0.52 wt % remainingSiH.

Release Coating with Anchorage Additive:

A release coating formulation prepared by mixing:

¹SL6625 500.0 g ¹SL6110-D1 500.0 g ¹SS4300c  23.0 g Example 2 Additive 30.0 g ¹GE Silicones solventless paper release product

This coating formulation above were coated² onto 142 gauge polyesterfilm (PET) corona treated to 54 dyne cm. Samples were cured for thetimes and the temperatures shown in Table 2 below. These were evaluatedafter 1 hour and 5 days room temperature aging for anchorage by a fingerrub-off method. ² Black Clawson Converting Machinery LLC, Fulton, N.Y.

TABLE 2 Abrasive Test of PET films Exit Web Web Speed, Dwell time, Temp,Initial 5-Day ft/min sec ° F. Rub off test Rub off test 100 9.0 239 +/−+/− 200 4.5 239 +++ +++ 300 3.0 245 +++ +++ 100 9.0 282 +++ +++ 200 4.5278 +++ +++ 300 3.0 275 +++ +++ 400 2.25 280 +++ +++ 100 9.0 328 +++ +++200 4.5 328 +++ +++ 300 3.0 325 +++ +++ 400 2.25 325 +++ +++

Efficiency of attachment by “rub-off” was rated as follows:

very weakly attached −−− weakly attached −− could be removed but notvery easy +/− strongly attached ++ very strongly attached +++

Example 3 Preparation of Anchorage Additives: Additive A

A mixture of allyl glycidyl ether (AGE) (Aldrich, 79.1 g, 0.69 mol) andpolydimethylmethylhydrosiloxane (200.0 g, SiH=1.05 wt %) and 20 ppmrhodium using an ethanol solution oftris(dibutylsulfide)rhodium(III)-trichloride containing 1.2 wt % rhodiumat 95-120° C. then held at 95-120° C. for 1 hour. The reaction mixturewas vacuum stripped at 120° C. to yield a 199 cstks reaction producthaving 0.48 wt % remaining SiH.

Additive B

A mixture of allyl glycidyl ether (AGE) (Aldrich, 89.8 g, 0.79 mol) andpolydimethylmethylhydrosiloxane (150.0 g, SiH=1.05 wt %) and 20 ppmrhodium using an ethanol solution oftris(dibutylsulfide)rhodium(III)trichloride containing 1.2 wt % rhodiumat 95-120° C. then held at 95-120° C. for 1 hour. The reaction mixturewas vacuum stripped at 120° C. to yield a 476 cstks reaction producthaving 0.24 wt % remaining SiH.

Additive C

A mixture of allyl glycidyl ether (AGE) (Aldrich, 662 g, 0.58 mol) andpolymethylhydrosiloxane (145.0 g, SiH=1.6 wt %) and vinytrimethoxysilane(86.0 g, 0.58 mol) and 20 ppm rhodium using an ethanol solution oftris(dibutylsulfide)rhodium(III)trichloride containing 1.2 wt % rhodiumat 95-145° C. then held at 95-110° C. for 2 hours. The reaction mixtureyielded a 185 cstks reaction product having 0.38 wt % remaining SiH.

Release Coating with Anchorage Additive:

A release coating formulation prepared by mixing:

¹SL6625 500.0 g ¹SL6110-D1 500.0 g ¹SS4300c  23.0 g Additive  30.0 g ¹GESilicones solventless paper release product

This coating formulation above were coated² onto 142 gauge polyesterfilm (PET) corona treated to 54 dyne cm. Samples were cured for thetimes and the temperatures shown in Table 3 below. These were evaluatedafter 72 hours exposed to maximum humidity at 60° C. aging for anchorageby a finger rub-off method. ² Black Clawson Converting Machinery LLC,Fulton, N.Y.

TABLE 3 Abrasive Test of PET films Web Speed, Dwell time, Exit Web Temp,Additive ft/min sec ° F. Rub off test A 325 2.8 269 ++ A 375 2.4 271 +++A 325 2.8 296 +++ A 375 2.4 296 +++ B 325 2.8 269 +++ B 375 2.4 269 +++B 325 2.8 298 +++ B 375 2.4 297 +++ C 300 3.0 276 −− C 400 2.25 279 −−

Efficiency of attachment by “rub-off” was rated as follows:

very weakly attached −−− weakly attached −− could be removed but notvery easy +/− strongly attached ++ very strongly attached +++

Example 4

A mixture of carbic anhydride (13.1 g, 0.08 mol) andpolymethylhydrosiloxane (100.0 g, SiH=1.6 wt %) and 25 ppm platinum asKarstdet catalyst and 230.0 g toluene refluxed at 100-107° C. for 5hours. The reaction mixture was vacuum stripped at 80° C. to yield areaction product having 1.35 wt % remaining SiH with about 7 mole %carboxylic acid anhydride functionality.

Release Coating with Anchorage Additive:

A release coating formulation prepared by mixing:

¹SL6625 500.0 g ¹SL6110-D1 500.0 g ¹SS4300c  23.0 g Additive  30.0 g

This coating formulation above were coated²onto 142 gauge polyester film(PET) corona treated to 54 dyne cm. Samples were cured for the times andthe temperatures shown in Table 3 below. These were evaluated after 72hours exposed to maximum humidity at 60° C. aging for anchorage by afinger rub-off method.

TABLE 4 Abrasive Test of PET films Web Speed, Dwell time, Exit Web Temp,ft/min sec ° F. Rub off test 150 6.0 256 +++ 200 4.5 249 +++ 300 3.0 253+++

Efficiency of attachment by “rub-off” was rated as follows:

very weakly attached −−− weakly attached −− could be removed but notvery easy +/− strongly attached ++ very strongly attached +++

Comparison Example 1 Comparison Additive:

An anchorage additive prepared per U.S. Pat. No. 3,873,334 comprised ofan epoxy functional silane and vinyltriacetoxysilane was evaluated at 1and 3 wt. % as in Example 1 above. Rub-off was observed at both additivelevels on non-adhesive and adhesive coated PET.

Example 5 Example 2 Additive Evaluated in a UV Cured Release Coating:

Qualitative determinations of the effect of Example 2 additive on cureand anchorage of UV curable epoxysilicone coatings were completed usinga Filcher Hamilton 2 mil PET substrate. Two UV cure coating formulationswere used in these experiments with the composition of Example 2 ascandidate anchorage additive.

Composition A: Mixture of 90 parts ¹UV9400 epoxysilicone+5 partsdodecylphenol+5 parts ¹UV9440E di-carbinol stopped silicone fluid+1.5parts ¹UV9385C iodonium photocatalyst solution.

Composition B: Mixture of 100 parts of dimethylepoxy-stopped linear D22length silicone polymer+2 parts ¹UV9380C sensitized iodoniumphotocatalyst solution.

Coatings ˜1.2 g/m² weight were manually applied to 2 mil PET substrates,then exposed to focused UV light from Hanovia medium pressure mercuryvapor lamps mounted in an RPC Model lab UV Processor. Samples wereaffixed to a carrier board and passed under the lamps on a conveyer.Total UV flux directed at the coatings was modulated by varying lamppower and conveyer speed to furnish either ˜65 mJ/cm² or ˜160 mJ/cm² UVflux. Coatings were examined for silicone migration to Scotch™ 610cellophane adhesive tape and for smear and nib-off (tendency of acoating to be readily removed from a substrate by light finger pressureor rub). Results and observations are given in Table 5 below.

Example 2 additive is incompletely miscible with compositions A & B, butformed stable cloudy mixtures when 3 parts were blended with 100 partsof coating. Qualitative results are tabulated below:

TABLE 5 Example 2 Coating Additive UV Flux Observation A None 65 mJCured - no migration, but very easy rub off With minimal pressure A None160 (same at 65 mJ) A 3 phr 65 Cure OK - slight migration noted, rub-offOnly with hard pressure A 3 phr 160 Excellent cure - no migration, verygood Anchorage (very hard rub-off) B None 65 Cured - no migration, hardrub-off (better anchorage than coating A) B 2 phr 65 Undercured -migration and smear noted B 3 phr 160 Excellent cure - no migration,very good Anchorage (very hard rub-off)

1-43. (canceled)
 44. A laminate having a substrate and a release coatingcoated upon said substrate, wherein said release coating comprises: (A)an additive for anchorage of a release coating, said additive being acompound of the general formula:(R_(a)SiO_((4−a)/2))_(n) where n is an integer greater than 3, a rangesfrom about 1 to about 3, R is independently selected from the groupconsisting of: oxirane containing radicals having from one to fortycarbon atoms, epoxide containing radicals having from one to fortycarbon atoms, carboxylic acid anhydride containing radicals having fromone to forty carbon atoms, monovalent hydrocarbon radicals, monovalenthydrocarbonoxy radicals, and hydride atoms, wherein at least one of saidoxirane or epoxide or carboxylic acid anhydride containing radicals arepresent per molecule, and wherein at least one of said hydride atoms arepresent per molecule; (B) a curable alkenyl silicone having the formulaM^(Vi) _(a)T_(b)D_(c)M_(d) where M^(Vi)=R¹ _(3−p)R² _(p)SiO_(1/2), whereR¹ is selected from the group consisting of one to forty carbonmonovalent hydrocarbon radicals and R² is selected from the groupconsisting of two to forty carbon atom terminal olefinic monovalenthydrocarbon radicals, where p ranges from 1 to 3; T=R³SiO_(3/2) where R³is selected from the group consisting of R¹ and R²; D=R⁴R⁵SiO_(2/2)where R⁴ and R⁵ are each independently selected from the groupconsisting of R¹ and R²; and M=R¹ ₃SiO_(1/2) where each R¹ is aspreviously defined and is independently selected; wherein a and b havevalues ranging from 2 to 5, c is an integer ranging from about 50 toabout 1,000 and d has a value ranging from 2 to about 0.5; and whereinsaid release coating composition is cured.
 45. The laminate of claim 44wherein at least one of said oxirane or epoxide containing radicals andat least one of said hydride atoms are present per molecule of saidcomponent (A) of said release coating.
 46. The laminate of claim 44wherein at least one of said carboxylic acid anhydride containingradicals and at least one of said hydride atoms are present per moleculeof said component (A) of said release coating.
 47. The laminate of claim44 wherein variable a of component (A) of the release coating is about3, and component (A) features at least one of said oxirane or epoxidecontaining radicals per molecule, at least one of said hydride atoms permolecule, and at least one of said hydrocarbonoxy radicals per molecule.48. The laminate of claim 44 wherein the subscripts a, b and d ofcomponent (B) of the release coating satisfy the relationship a+d>b. 49.The laminate of claim 48 wherein the viscosity of component (B) of therelease coating ranges from about 100 to about 10,000 centipoise. 50.The laminate of claim 48 wherein the viscosity of component (B) of therelease coating ranges from about 125 to about 1,000 centipoise.
 51. Thelaminate of claim 44 wherein the release coating additionally contains ahydrogen siloxane selected from the group of compounds:MD_(e)D′_(f)M,MD′_(f)M,MD_(e)D′_(f)M′,M′D_(e)D′_(f)M, andM′D_(e)M′, where M=R′₃SiO_(1/2), M′=H_(g)R′_(3−g)SiO_(1/2), andD=R′R′SiO_(2/2), and D′=R′HSiO_(2/2) where each R′ in M, M′ D, and D′ isindependently selected from the group consisting of one to forty carbonmonovalent hydrocarbon radicals wherein the subscripts e and f may bezero or positive whereby the sum of e and f ranges from about 10 toabout 100 subject to the limitation that the sum of f and g is two orgreater.
 52. The laminate of claim 51 where R¹ is methyl,trifluoropropyl or phenyl and R² is selected from the group consistingof two to ten carbon atom alkenyl groups.
 53. The laminate of claim 51wherein where R′ is methyl, trifluoropropyl or phenyl.
 54. The laminateof claim 51 wherein the hydrogen siloxane is selected from the groupsconsisting ofMD_(e)D′_(f)M,MD′_(f)M, and mixtures thereof, wherein the subscripts e and f may bezero or positive whereby the sum of e and f ranges from about 10 toabout 100 subject to the limitation that f is two or greater.
 55. Thelaminate of claim 44 further comprising at least one component selectedfrom the group consisting of bath life extenders, release additives,fillers, extenders, photocatalysts, reactive diluents, anchorageadditives.
 56. The laminate of claim 44 wherein said substrate isselected from the group consisting of paper and polymeric films
 57. Thelaminate of claim 56 wherein said substrate is selected from the groupconsisting of polyethylene, polypropylene, and polyester.
 58. A laminatehaving a substrate and a release coating coated upon said substrate,wherein said release coating comprises: (A) an additive for anchorage ofa release coating, said additive being a compound of the generalformula:(R_(a)SiO_((4−a)/2))_(n) where n is an integer greater than 3, a rangesfrom about 1 to about 3, R is independently selected from the groupconsisting of: oxirane containing radicals having from one to fortycarbon atoms, epoxide containing radicals having from one to fortycarbon atoms, carboxylic acid anhydride containing radicals having fromone to forty carbon atoms, monovalent hydrocarbon radicals, monovalenthydrocarbonoxy radicals, and hydride atoms, wherein at least one of saidoxirane or epoxide or carboxylic acid anhydride containing radicals arepresent per molecule, and wherein at least one of said hydride atoms arepresent per molecule; (B) a curable alkenyl silicone having the formulaM^(Vi) _(a)T_(b)D_(c)M_(d) where M^(Vi)=R¹ _(3−p)R² _(p)SiO_(1/2), whereR¹ is selected from the group consisting of one to forty carbonmonovalent hydrocarbon radicals and R² is selected from the groupconsisting of two to forty carbon atom terminal olefinic monovalenthydrocarbon radicals, where p ranges from 1 to 3; T=R³SiO_(3/2)where R³is selected from the group consisting of R¹ and R²; D=R⁴R⁵SiO_(2/2)where R⁴ and R⁵ are each independently selected from the groupconsisting of R¹ and R²; and M=R¹ ₃SiO_(1/2) where each R¹ is aspreviously defined and is independently selected; wherein a and b havevalues ranging from 2 to 5, c is an integer ranging from about 50 toabout 1,000 and d has a value ranging from 2 to about 0.5; (C) ahydrogen siloxane selected from the group of compounds;MD_(e)D′_(f)M,MD′_(f)M,MD_(e)D′_(f)M′,M′D_(e)D′_(f)M, andM′D_(e)M′, where M=R′₃SiO_(1/2), M′=H_(g)R′_(3−g)SiO_(1/2), andD=R′R′SiO_(2/2), and D′=R′HSiO_(2/2) wherein each R′ in M, M′, D, and D′is independently selected from the group consisting of one to fortycarbon monovalent hydrocarbon radicals wherein the subscripts e and fmay be zero or positive whereby the sum of e and r ranges from about 10to about 100 subject to the limitation that the sum of f and g is two orgreater; (D) a hydrosilylation catalyst; and (E) an inhibitor, andwherein said release coating composition is cured.
 58. The laminate ofclaim 57 wherein at least one of said oxirane or epoxide containingradicals and at least one of said hydride atoms are present per moleculeof said component (A) of said release coating.
 59. The laminate of claim57 wherein at least one of said carboxylic acid anhydride containingradicals and at least one of said hydride atoms are present per moleculeof said component (A) of said release coating.
 60. The laminate of claim57 wherein variable a of component (A) of the release coating is about3, and component (A) features at least one of said oxirane or epoxidecontaining radicals per molecule, at least one of said hydride atoms permolecule, and at least one of said hydrocarbonoxy radicals per molecule.61. The laminate of claim 57 wherein the subscripts a, b and d ofcomponent (B) of the release coating satisfy the relationship a+d>b. 62.The laminate of claim 61 wherein the viscosity of component (B) of therelease coating ranges from about 100 to about 10,000 centipoise. 63.The laminate of claim 61 wherein the viscosity of component (B) of therelease coating ranges from about 125 to about 1,000 centipoise.
 64. Thelaminate of claim 57 where R′ is methyl, trifluoropropyl or phenyl andR² is selected from the group consisting of two to ten carbon atomalkenyl groups.
 65. The laminate of claim 57 wherein where R′ is methyl,trifluoropropyl or phenyl.
 66. The laminate of claim 57 wherein thehydrogen siloxane is selected from the groups consisting ofMD_(e)D′_(f)M,MD′_(f)M, and mixtures thereof, wherein the subscripts e and f may bezero or positive whereby the sum of e and f ranges from about 10 toabout 100 subject to the limitation that f is two or greater.
 67. Thelaminate of claim 57 further comprising at least one component selectedfrom the group consisting of bath life extenders, release additives,fillers, extenders, photocatalysts, reactive diluents, anchorageadditives.
 68. The laminate of claim 57 wherein said substrate isselected from the group consisting of paper and polymeric films
 69. Thelaminate of claim 68 wherein said substrate is selected from the groupconsisting of polyethylene, polypropylene, and polyester.